Plant growth regulators

ABSTRACT

1. A PLANT GROWTH REGULATORY COMPOSITION COMPRISING AN EFFECTIVE AMOUNT OF 2- (N,N,N- TRIMETHYLAMINO) ETHYL-CHRYSANTHEMUMATE CHLORIDE AND AN INERT CARRIER.

United States Patent 3,846,112 PLANT GROWTH REGULATORS Llewellyn W.Fancher, Orinda, Calif., assignor to Staul't'er Chemical Company, NewYork, N.Y.

No Drawing. Original application Apr. 2, 1970, Ser. No. 25,296, nowPatent No. 3,701,799. Divided and this application May 15, 1972, Ser.No. 253,092

Int. Cl. A01n 9/20 US. Cl. 7176 7 Claims ABSTRACT OF THE DISCLOSURENovel esters of crysanthemumic acid are disclosed. The compounds areuseful as plant growth regulators.

SUMMARY OF THE INVENTION This is a division of application Ser. 'No.25,296 filed Apr. 2, 1970, now US. Pat. 3,701,799.

This invention relates to novel compositions of matter and their use asplant growth regulators. More particularly, this invention relates tocompounds having the formula:

wherein R R and R are selected independently from the group consistingof alkyl containing 1 through 6 carbon atoms, cycloalkyl containing 4through 6 carbon atoms, alkenyl containing 2 through 6 carbon atoms,alkynyl containing 2 through 6 carbon atoms, benzyl, halobenzyl, phenyland halophenyl; R is alkylene containing 1 through 6 carbon atoms; and Xis a member selected from the group consisting of chlorine, bromine, andiodine, and the use of these materials as plant regulators. Except asotherwise indicated, the terms halogen or halo used in describing theinvention encompass chlorine, bromine, and iodine and include monoandpolysubstitution. In a preferred form, the invention relates tocompounds having the formula:

wherein R R and R are selected independently from the group consistingof alkyl containing 1 through 6 carbon atoms, alkenyl containing 2through 6 carbon atoms, benzyl, halobenzyl, phenyl and halophenyl; R isalkylene containing 1 through 3 carbon atoms; and X is a member selectedfrom the group consisting of chlorine, bromine, and iodine. In thisembodiment, any halo-substitution is preferably monoor di-halo. In itsmost preferred form, the invention relates to compounds having theformula:

wherein R R; and R are selected independently from the group consistingof alkyl containing 1 through 3 carbon atoms, phenyl, and halophenylcontaining not more than two halogen atoms; R is alkylene containing 1through 3 carbon atoms, and X is selected from the group consisting ofchlorine, bromine, and iodine; and the use of these materials as plantgrowth regulators. The

3,846,] 12 Patented Nov. 5, 1974 term plant growth regulator or variantsthereof, and as employed throughout the specification and claims, isused to describe those materials which exhibit certain effects on thegrowth habits of plants, including, but not limited thereto, dwarfing orstunting, regulation of the onset of flowering and the number of flowersproduced, regulation of amount of fruit set, defoliation, reduction orin hibition of lateral growth, and shortening of internodes. Plantgrowth regulators, for example, may be used as stunting agents ongrasses, thus allowing extended periods between grass cutting, whilemaintaining favorable landscape conditions. On certain crop species,greater pod yield allows increased production.

Compounds of the invention wherein R R and R are independently alkyl,cycloalkyl containing 4 through 6 carbon atoms, alkenyl, alkynyl,benzyl, and halobenzyl, and R is alkylene containing 1 to 6 carbonatoms, as indicated, may be prepared by the following general reactions:

CH3 CH3 pyridine CH3 CH3 R4 CH3 Compounds of the invention wherein R Rand R are independently phenyl or halophenyl are more suitably preparedby the following general reactions:

In the first described series in which R R and R are non-aryl, thestarting hydroxyamine salts, where not easily available, may be preparedby the following general reaction:

may be prepared easily by reacting (CH NCH CH OH with CH I.

The concentrations of the reactants employed are not particularlycritical, although normally an excess of the pyridine will be employed.In general, approximately equimolar amounts may be employed. Thereactions are generally carried out in a suitable inert solvent, such asbenzene, acetone, dioxane, etc. Reactions of this type are exothermic,so that the addition of heat is not required and, in actuality, coolingmay sometimes be necessary to control the reaction rate. The reactionswill normally be carried out at temperatures of from about C. to about25 C. Pressures may be atmospheric, subatmospheric, or greater thanatmospheric, as desired. Preparation of the compounds of the inventionis illustated by the following examples:

EXAMPLE I Preparation of 2- (N,N,N-trimethylamino)ethylchrysanthemumatechloride Approximately 7.0 grams (0.05M) of choline chloride issuspended in 50 cc. of CHCl and 7.2 grams (0.09M) of pyridine. About11.4 grams (0.06M) of chrysanthemumic chloride is added while keepingthe temperature below C. The mixture is allowed to stand at roomtemperature for about 18 hours. The mixture is then heated to about 60C., evaporated and the residue is taken up in 50 cc. of methanol. About13.2 grams (0.06M) of percent NaOCH is added and the temperature ismaintained below 20 C. for about 5 minutes. The mixture is then filteredand evaporated to give Z-trimethylaminoethylchrysanthemumate chloride.

EXAMPLE II Preparation of 3(N,N-diethyl,N-propylamino)propylchrysanthemumate chloride The procedure of Example Iis repeated, except that 69 [(n-CaH7) (C2H5)zNCH2CHzCH2OH]1 issubstituted for the choline chloride.

EXAMPLE III Preparation of 2-(N,N-diethyl,N-a-allylamino)ethylchrysanthemumate chloride The procedure of Example Iis repeated, except that GB [(02155)2(CHz=CHCHz)NCHzCHzOH]l issubstituted for the choline chloride.

EXAMPLE IV Preparation of 2-(N,N-diethyl, N-ethynylamino)ethy1chrysanthemumate chloride The procedure of Example I is repeated, exceptthat GB 6 l(CzH5)2( CH2CH2OH]OI is substituted for the choline chloride.

EXAMPLE V Preparation of 2-(N,N,N-tributenylamino)ethylchrysanthemumatebromide The procedure of Example I is repeated, except thatKCHZ=CHCH2CH2 3CH2CIIZ 0111?:

is substituted for the choline chloride.

EXAMPLE VI Preparation of (N,N-dimethyl, N-benzylamino)methylchrysanthemumate chloride The procedure of Example I isrepeated, except that is substituted for the choline chloride.

4 EXAMPLE vrr Preparation of 2-(N,N-dimethyl, N-p-chlorobenzylamino)ethyl-chrysanthemumate chloride The procedure of Example I is repeated,except that is substituted for the choline chloride.

EXAMPLE VIII Preparation of 2(N,N,N-triphenylamino)ethylchrysanthemumateiodide About 10.3 grams of chrysanthemumic chloride, 12 grams ofethylene Iodohydrin, and 25 cc. of benzene are combined and allowed tostand for approximately 48 hours. The mixture is then evaporated, takenup in benzene, washed with H O, aqueous NaHCO dried with MgSO and againevaporated to produce CH CH3 About 17.4 grams (0.054M) of this productis mixed with cc. of acetone, cooled to -30 C., and 13.2 grams (0.054M)of triphenylamine at 5 C. are added. The mixture is allowed to come toroom temperature and stand for about 48 hours. The mixture is thenevaporated, slurried in ether, filtered, and dried in a desiccator toproduce 2-(N,N,N triphenylamino)ethyl-chrysanthemumate Iodide.

EXAMPLE IX Preparation of2-(N,N,N-tri-p-chlorophenylamino)ethylchrysanthemumate Iodide Theprocedure of Example VIII is repeated, except that (p-chlorophenyl) N issubstituted for the triphenylamine.

Compounds which may be produced accordng to the invention include: 1

2-(N,N,N-trimethylamino)ethyl-chrysanthemumate chloride 2 (N,N,Ntrimethylamino)ethyl chrysanthemumate iodide 2 (N,N,Ntrimethylamino)ethyl chrysanthemumate bromide 3 (N,N,Ntriethylamino)propyl chrysanthemumate chloride 3-(N,N-dihexyl, N methyl'amino)propyl chrysanthemumate bromide 3 (N,N,N triphenylamino)propylchrysanthemumate bromide 2 (N,N-diethyl, N ethynylamino)ethylchrysanthemumate chloride I 2 (N cyclopentyl, N,N-di-methylamino)ethylchrysanthemumate chloride 2 (N methyl,N-ethyl,N-butylamino)ethyl-chrysanthemumate chloride 3 (N,N-diethyl,Npropylamino)propyl chrysanthemumate chloride 4 (NcyclohexyLN,N-dimethylamino)butyl chrysanthemumate chloride 2 (N,N,Ntriphenylamino)ethyl chrysanthemumate:

bromide 2 (N,N,N triphenylamino)ethyl chrysanthemumate chloride2-(N,N-diethyl,N allylaminoethyl chrysanthemumate chloride(N,N-dimethyl,N benzylamino)methyl chrysanthemumate chloride (N-ethyl,N,N-dibenzylamino)methyl-chugsarrtljemmnate chloride 2 (N,N,Ntribenzylamino)ethyl chrysanthemumate chloride 2(N,N-dimethyl,N-p-chlorobenzylamino)ethyl chrysanthemumate iodide 2(N,N,N-p-tri-chlorophenylamino)ethyl chrysanthemumate iodide 2(N,N,N-p-tri-chlorophenylamino)ethyl chrysanthemumate chloride 2(N,N,N-p-tri-bromophenylamino)ethyl chrysanthemumate bromide In order todemonstrate utility, the compound 2- (N,N,N-trimethylamino)ethyl-chrysanthemumate chloride was tested for plantgrowth regulatory activity as exemplary of the compounds of theinvention, in the following series of tests.

EXAMPLE X Metal flats were filled with loamy sand soil and sown withseeds of the crops, both grasses and broad leaf, indicated below in thetable. The test compound was applied at a rate of about five (5) poundsper acre, ten days after sowing. The compound was applied by mixing 750ml. of the test compound in 100 milliliters of a 50/50 Water, acetonesolution containing 1% Tween (polyoxyethylene sorbitan monolaurate).Ratings were taken approximately three weeks after application of thetest compound by comparing growth of the treated plant foliage withuntreated controls. The results are shown in the table below:

TABLE I Type of Regulation and Extent Stunting, percent Corn (Zea maysL.) 20

Milo 40 Cotton (Gossypium hirsutum L.) 20

Peas (Pisum sativum) 40 Sunflower (Helianthus annuus L.) 90

Cabbage (Brassica oleracea var. Capitata) 20 EXAMPLE XI The procedureemployed in this example was similar to that of Example X, except thatthe test compound was applied at a rate of about two (2) pounds per acreto soybeans (first trifoliate stage) and cucumbers (third leaf stage).The results, recorded three (3) Weeks after application, are shown inthe table below:

TABLE H As may be seen by the test results, the compounds of theinvention are useful in regulating the growth habits of plants.Preferably, the compounds are applied directly to the plants to bemodified, although they may also be applied to a locus before emergenceof the species to be regulated. It is necessary, of course, that theplants or locus receive an effective or regulating amount, i.e., anamount sufficient to give the desired plant growth regulating effect.Since the amount of active agent required will vary to some extent,depending on the plant treated, precise limits on the amounts employedcannot be given. The tests set forth above indicate exemplary amountswhich may be used, as will readily be appreciated by those of skill inthe art. Determination of the optimum effective concentration for aspecific application is readily conducted by routine procedures, as willalso be apparent to those skilled in the art.

The compounds are normally employed with a suitable carrier and may beapplied as a dust, spray, drench, or aerosol. The compounds thus may beapplied in combination with solvents, diluents, various surface activeagents (for example detergents, soaps, or other emulsifying or wettingagents, surface active clays) carrier media, adhesives, spreadingagents, humectants and the like. They may also be combined with otherbiologically active compositions, including fungicides, bactericides,and algaecides, insecticides, etc., as well as with fertilizers, soilmodifiers, etc. The compounds of the invention may be used incombination with an inert carrier and a surface active or emulsifyingagent, and may also be applied in combination with other biologicallyactive materials, in conjunction with a carrier and a surface active oremulsifying agent. The solid and liquid formulations can be prepared byany of the conventional methods well-known by those skilled in the art.

Various changes and modifications may be made without departing from thespirit and the scope of the invention described herein, as will beapparent to those skilled in the art to which it pertains.

I claim:

1. A plant growth regulatory composition comprising an effective amountof 2 (N,N,N Trimethylamino) ethyl-chrysanthemumate chloride and an inertcarrier.

2. A plant growth stunting composition comprising an effective amount of2- (N,N,N-trimethylamino) ethylchrysanthemumate chloride and an inertcarrier.

3. A method of stunting the growth of plants comprising applying to theplants an effective amount of 2-(N,N, N-trimethylamino)ethyl-chrysanthemumate chloride.

4. A method of regulating the growth habit of plants comprising applyingto the plants an effective amount of 2-(N,N,N-trimethylamino) ethylchrysanthemumate chloride.

5. A method of regulating the growth habit of plants comprising applyingto the plants an efiectve amount of a compound having the formulawherein X is a member selected from the group consisting of chlorine,bromine, and iodine.

6. A method of regulating the growth habit of plants comprising applyingto a locus to be regulated an effective amount of2-(n,n,n-trimethyamino) ethyl chrysanthemumate chloride.

7. A method of regulating the growth habit of plants comprislng applyingto a locus to be regulated an effective amount of a compound having theFormula on: on,

cm 0 0 cm I CHa;NCH CH -0 don on-on: o X CH3 CH3 wherein x is memberselected from the group consisting of Chlorine, bromine and iodine.

References Cited UNITED STATES PATENTS 3,395,009 7/1968 Oeltel et al.7l76 3,156,555 11/1964 Tolbert 7l67 3,156,554 11/1964 Tolbert 71-673,440,245 4/1969 Kato et a1 260-28l LEWIS GOTTS, Primary Examiner C. L.MILLS, Assistant Examiner US. Cl. X.R. 71-70, 106

1. A PLANT GROWTH REGULATORY COMPOSITION COMPRISING AN EFFECTIVE AMOUNTOF 2- (N,N,N- TRIMETHYLAMINO) ETHYL-CHRYSANTHEMUMATE CHLORIDE AND ANINERT CARRIER.